CN112499628A - Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture - Google Patents
Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture Download PDFInfo
- Publication number
- CN112499628A CN112499628A CN202011377274.4A CN202011377274A CN112499628A CN 112499628 A CN112499628 A CN 112499628A CN 202011377274 A CN202011377274 A CN 202011377274A CN 112499628 A CN112499628 A CN 112499628A
- Authority
- CN
- China
- Prior art keywords
- biomass
- carbon
- based porous
- carbon material
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3491—Regenerating or reactivating by pressure treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
Abstract
The invention discloses a biomass-based porous carbon material, a preparation method thereof and application of the material in separating 1, 3-butadiene from a carbon tetraene mixture. The method mainly comprises the following steps: carrying out hydrothermal carbonization on a biomass carbon source and an organic acid aqueous solution, carrying out ion exchange on an obtained carbon precursor and a quantitative alkali liquor, and then placing the obtained carbon precursor in a tubular furnace for carbonization and activation. The biomass-based porous material prepared by the invention is a microporous carbon material with a stable structure, and has the advantages of wide range of raw materials, low price, simple preparation process and excellent regeneration of the material. More importantly, the high-purity 1, 3-butadiene can be separated from the carbon tetraolefin component, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the field of adsorption separation materials, and particularly relates to a method for selectively separating 1, 3-butadiene from carbon-tetraolefin mixed gas by using a biomass-based porous carbon material and application thereof.
Background
1, 3-butadiene, which is one of the basic organic feedstocks used to produce various synthetic rubbers and chemicals, is of high commercial value, mainly from steam cracking of naphtha, catalytic cracking of gas oil, and carbon tetraolefin mixtures of Methanol To Olefins (MTO) processes. Whereas the mixed gas mainly contains 1-butene, isobutene and 1, 3-butadiene, and these components have similar physical and chemical properties (such as boiling point and polarizability).
In order to meet the requirement of high purity of 1, 3-butadiene for downstream processes, the industry generally needs to adopt an extractive distillation method and a solvent absorption method for component separation. As reported in patent US20190233351a1, a carbon tetrad stream comprising 1, 3-butadiene and acetylene is introduced into an organic azide for extractive distillation and 1, 3-butadiene is distilled from the resulting triazole comprising stream. Furthermore, patent US6040489 reports the separation of a carbon tetrahydrocarbon stream containing 1, 3-butadiene by extractive distillation with addition of acetonitrile and N, N-dimethylformamide. However, the traditional process needs a large amount of organic solvent and has high energy consumption, and the environment is easily polluted.
Compared with the large-scale industrial distillation process with high energy consumption, the method for adsorbing and separating the carbon tetraolefin component by using the porous adsorbent is an energy-saving and efficient purification method. Adsorption separation is centered on the performance of the adsorbent. By designing the pore structure of the adsorption material, the adsorption material is adapted to the physical and chemical properties (such as molecular dynamic diameter, polarizability, dipole moment and the like) of different guest molecules, and high-selectivity adsorption separation is realized. The adsorbents reported to date for separating the carbon tetraolefins are mainly zeolite molecular sieves and metal organic framework Materials (MOFs). Patent US3992471 reports the use of sodium or potassium ion loading on exchangeable cationic sites of zeolite X to achieve selective separation of 1, 3-butadiene in a tetracarbon stream, but its separation capacity at low diene partial pressures has not been able to meet today's purity requirements. Gucuyener et al used DD3R zeolite treated with KOH and KF for adsorptive separation of 1, 3-butadiene and 1-butene isomers with 1, 3-butadiene/1-butene selectivities of about 4-7 at 30 ℃ (J.Mater. chem.,2011,21(45): 18386-18397.). However, the preparation period of the DD3R zeolite is relatively long, which is not favorable for industrial popularization.
MOFs have the characteristics of adjustable aperture, strong chemical modifiability and the like. Zhang et al invented a series of MOFs with copper coordination network GeFSIX-2-Cu-i (ZU-32) interpenetrating through anionic posts that fine-tune the cavities and functional sites, where GeFSIX-14Cu-i showed an adsorption capacity of 2.67mmol/g for 1, 3-butadiene at 1.01bar and 25 ℃, and 1, 3-butadiene/1-butene, 1, 3-butadiene/isobutylene selectivities of 4.68 and 6.40, respectively (Angew. chem. int. Ed.,2017,129(51): 16500-. However, at present, the MOFs materials face the problems of structural stability and production cost, and still need a long time to be industrialized.
At present, most of the research on the adsorption and separation of 1, 3-butadiene focuses on zeolite and MOFs materials, and the problems of adsorption capacity and dynamic separation performance are not completely solved. Meanwhile, studies on the separation of tetraolefins using carbon materials as the adsorbent have been reported. Therefore, new methods and materials for separating 1, 3-butadiene from a mixture of carbon tetraolefins are urgently needed.
The invention content is as follows:
the invention aims to provide a method for separating a carbon tetraolefin mixture with high selectivity by using a biomass-based porous microporous carbon material. The porous carbon material prepared by the method has high adsorption separation selectivity of the carbon tetraolefin mixture, good stability, developed pore structure, wide raw material source, low price and reproducibility.
The purpose of the invention is realized by the following technical scheme.
A method of preparing a biomass-based porous carbon material, comprising the steps of:
(1) mixing a biomass carbon source and an organic acid aqueous solution in proportion, uniformly stirring, and then placing in a high-pressure reaction kettle for carrying out constant-temperature dehydration condensation polymerization reaction to obtain a carbon precursor;
(2) washing and drying the carbon precursor obtained in the step (1), adding the carbon precursor into an alkaline activator aqueous solution, and carrying out an ion exchange reaction under the conditions of heating and stirring;
(3) and (3) washing and drying the solid material obtained in the step (2), protecting the solid material in an inert atmosphere, carrying out high-temperature carbonization activation reaction in a tubular furnace, and then washing the solid material with dilute hydrochloric acid and water respectively to obtain the biomass-based microporous carbon material.
Further, in the step (1), the biomass carbon source is a carbohydrate; the saccharide substance comprises more than one of corn starch, potato starch, pea starch, sucrose and fructose; the mass ratio of the biomass carbon source to the organic acid is 1 (0.05-0.2);
further, in the step (1), the temperature of the dehydration condensation polymerization reaction is 180-230 ℃; the time of the dehydration condensation polymerization reaction is 10-20 h.
Further, in the step (2), the alkaline activator is one or more of NaOH, KOH, RbOH or CsOH, and the molar ratio of the alkaline activator to the organic acid is 1: (0.5 to 1).
Further, in the step (2), the temperature of the ion exchange reaction is 40-100 ℃; the time of the ion exchange reaction is 6-24 h.
Further, in the step (3), the inert atmosphere is argon, nitrogen or a mixed gas of argon and nitrogen in any proportion.
Further, in the step (3), the temperature of the high-temperature activation reaction is 700-900 ℃.
Further, in the step (3), the time of the high-temperature activation reaction is 1-4 h.
A biomass-based carbon material is applied to separation of 1, 3-butadiene from a carbon tetraolefin mixture, and comprises the following steps: firstly, the adsorbing material is loaded in an adsorption bedWithin the layer, a stream of tetraolefins is passed, which, due to size sieving and steric effects, is composed of only 1, 3-butadiene of smaller molecular size (kinetic diameter:
) Can be adsorbed in the pores of the material, while 1-butene, which is larger in molecular size (kinetic diameter:
) And isobutylene (kinetic diameter:
) Will flow out from the bed layer; then, the pure component of the 1,3 butadiene can be obtained by elution in the bed layer through the next step of pressure swing regeneration desorption process; the regenerated biomass-based adsorption material is used for the next adsorption separation process and is recycled; the method avoids the high energy consumption process required by low-temperature distillation and has very important industrial application value.
The invention innovatively provides a method for separating a carbon tetraene mixture by using a bio-based porous carbon material. The method adopts cheap biomass as a raw material, prepares a high-selectivity adsorbent with the characteristic of preferentially adsorbing 1, 3-butadiene by series of processes such as polymerization, carbonization, ion exchange and activation and system optimization in the presence of an organic additive, and applies the high-selectivity adsorbent to the separation of the carbon-tetraolefin mixture, and the adsorbent can realize 1, 3-butadiene adsorption capacity of more than 2.2mmol/g and almost exclude 1-butene and isobutene through different ion activation regulation. The adsorbent also has the advantages of stable structure and low cost, and is an adsorption separation material for separating the carbon-four-olefin mixture with good industrial application prospect.
Compared with the prior art, the invention has the following advantages:
the invention provides a method for adsorbing and separating a carbon-tetraolefin mixture by using a bio-based porous carbon material for the first time, which can realize high-selectivity separation of 1, 3-butadiene from the carbon-tetraolefin mixture and has excellent 1, 3-butadiene adsorption performance. Meanwhile, the adsorbing material prepared by the method selects cheap biomass as a carbon source, and has the advantages of environmental protection and reproducibility. In addition, compared with the traditional high-energy-consumption and easy-pollution modes such as extractive distillation, solvent absorption and the like, the adsorption separation method provided by the invention has the outstanding advantages of cleanness, greenness, small equipment investment and the like, thereby having good industrial application prospect.
Drawings
Fig. 1 is a scanning electron micrograph of the biomass-based porous carbon material obtained in example 1.
Fig. 2 is a thermogravimetric plot of the biomass-based porous carbon material obtained in example 1.
Fig. 3 is a scanning electron micrograph of the biomass-based porous carbon material obtained in example 2.
Fig. 4 is an adsorption isotherm of the carbonitridiene component by the biomass-based porous carbon material obtained in example 2.
Fig. 5 is an adsorption isotherm of the carbonitridiene component by the biomass-based porous carbon material obtained in example 3.
Detailed Description
The invention will be further described with reference to the drawings and the detailed description, to which the invention is not restricted.
Example 1
6g of corn starch and 0.66g of acrylic acid were added to 60mL of distilled water and mixed. After being dispersed uniformly, the mixture is transferred into a high-pressure reaction kettle to carry out hydrothermal polymerization reaction for 14h at 190 ℃, and the obtained carbon precursor is subjected to vacuum filtration and water washing. Then adding the carbon precursor into the mixture to be mixed with 0.16mol/L NaOH solution, stirring the mixture at the temperature of 60 ℃ for reaction for 12 hours, then washing and drying the mixture, putting the mixture into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, raising the temperature to 800 ℃ under the protection of nitrogen, carrying out activation reaction for 1.5 hours, cooling the mixture, carrying out acid washing by using 1mol/L diluted hydrochloric acid, washing the mixture to be neutral by using distilled water, and drying the mixture to obtain the biomass-based porous carbon material.
The scanning electron microscope image of the material prepared in the example is shown in fig. 1, and the material still has uniform and complete spherical morphology after high-temperature carbonization and activation.
The thermogravimetric graph of the material prepared in the example is shown in FIG. 2, and has excellent thermal stability.
Example 2
6g of corn starch and 0.66g of acrylic acid were added to 60mL of distilled water and mixed. After being dispersed uniformly, the mixture is transferred into a high-pressure reaction kettle to carry out hydrothermal polymerization reaction for 14h at 190 ℃, and the obtained carbon precursor is subjected to vacuum filtration and water washing. Then, adding the carbon precursor into the mixture to be mixed with 0.16mol/L KOH solution, stirring the mixture at the temperature of 60 ℃ for reaction for 10 hours, then washing and drying the mixture, putting the mixture into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, raising the temperature to 800 ℃ under the protection of nitrogen, carrying out activation reaction for 1.5 hours, cooling the mixture, carrying out acid washing by using 1mol/L diluted hydrochloric acid, washing the mixture to be neutral by using distilled water, and drying the mixture to obtain the biomass-based porous carbon material.
The scanning electron microscope image of the material prepared in the example is shown in fig. 3, and the material still has uniform and complete spherical morphology after high-temperature carbonization and activation.
The adsorption isotherm of the tetraolefin component at 298K for the material prepared in this example is shown in FIG. 4, and the material has a high adsorption capacity (2.39mmol/g) for 1, 3-butadiene at 298K at 1bar, and almost excludes 1-butene and isobutene.
Example 3
6g of potato starch, 0.66g of acrylic acid were added to 60mL of distilled water and mixed. After being dispersed uniformly, the mixture is transferred into a high-pressure reaction kettle to carry out hydrothermal polymerization reaction for 14h at 190 ℃, and the obtained carbon precursor is subjected to vacuum filtration and water washing. Then, adding the carbon precursor into the mixture to be mixed with 0.16mol/L KOH solution, stirring the mixture at the temperature of 60 ℃ for reaction for 10 hours, then washing and drying the mixture, putting the mixture into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, raising the temperature to 800 ℃ under the protection of nitrogen, carrying out activation reaction for 1.5 hours, cooling the mixture, carrying out acid washing by using 1mol/L diluted hydrochloric acid, washing the mixture to be neutral by using distilled water, and drying the mixture to obtain the biomass-based porous carbon material.
The adsorption isotherm of the tetraolefin component at 298K for the material prepared in this example is shown in FIG. 4, and the material has a high adsorption capacity (2.64mmol/g) for 1, 3-butadiene at 298K at 1bar, and almost excludes 1-butene and isobutene.
Example 4
6g of pea starch, 0.66g of acrylic acid were added to 60mL of distilled water and mixed. After being dispersed uniformly, the mixture is transferred to a high-pressure reaction kettle to carry out hydrothermal polymerization reaction for 20 hours at the temperature of 180 ℃, and the obtained carbon precursor is subjected to vacuum filtration and water washing. Then, adding the carbon precursor into the mixture to be mixed with 0.16mol/L KOH solution, stirring the mixture at the temperature of 60 ℃ for reaction for 16 hours, then washing and drying the mixture, then placing the mixture into a porcelain boat, placing the porcelain boat into a high-temperature tube furnace, raising the temperature to 900 ℃ under the protection of nitrogen, then carrying out activation reaction for 1 hour, cooling the mixture, carrying out acid washing by using 1mol/L diluted hydrochloric acid, washing the mixture to be neutral by using distilled water, and drying the mixture to obtain the biomass-based porous carbon material.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a biomass-based porous carbon material is characterized by comprising the following steps:
(1) mixing a biomass carbon source and an organic acid aqueous solution in proportion, uniformly stirring, and then placing in a high-pressure reaction kettle for carrying out constant-temperature dehydration condensation polymerization reaction to obtain a carbon precursor;
(2) washing and drying the carbon precursor obtained in the step (1), adding the carbon precursor into an alkaline activator aqueous solution, and carrying out an ion exchange reaction under the conditions of heating and stirring;
(3) and (3) washing and drying the solid material obtained in the step (2), protecting the solid material in an inert atmosphere, carrying out high-temperature carbonization activation reaction in a tubular furnace, and then washing the solid material with dilute hydrochloric acid and water respectively to obtain the biomass-based microporous carbon material.
2. The method for producing a biomass-based porous carbon material according to claim 1, wherein in the step (1), the biomass carbon source is a saccharide; the saccharide substance comprises more than one of corn starch, potato starch, pea starch, sucrose and fructose; the mass ratio of the biomass carbon source to the organic acid is 1 (0.05-0.2).
3. The method for preparing a biomass-based porous carbon material according to claim 1, wherein in the step (1), the temperature of the dehydration condensation polymerization reaction is 180 to 230 ℃; the time of the dehydration condensation polymerization reaction is 10-20 h.
4. The method of claim 1, wherein in the step (2), the alkaline activator is one or more of NaOH, KOH, RbOH or CsOH, and the molar ratio of the alkaline activator to the organic acid is 1: (0.5 to 1).
5. The method for preparing a biomass-based porous carbon material according to claim 1, wherein in the step (2), the temperature of the ion exchange reaction is 40 to 100 ℃; the time of the ion exchange reaction is 6-24 h.
6. The method for producing a biomass-based porous carbon material according to claim 1, wherein in the step (3), the inert atmosphere is argon, nitrogen or a mixed gas of argon and nitrogen in any ratio.
7. The method for preparing a biomass-based porous carbon material according to claim 1, wherein the temperature of the high-temperature activation reaction in the step (3) is 700 to 900 ℃.
8. The method for preparing a biomass-based porous carbon material according to claim 1, wherein in the step (3), the time of the high-temperature activation reaction is 1-4 h.
9. A biomass-based carbon material produced by the method of any one of claims 1 to 8.
10. The application of the biomass-based carbon material of claim 9 in separating 1, 3-butadiene from carbon tetraolefin mixture is characterized by comprising the following steps: the adsorption material is firstly filled in an adsorption bed layer, and then carbon tetraolefin flow is introduced, and only 1, 3-butadiene (kinetic diameter:
) Can be adsorbed in the pores of the material, while 1-butene, which is larger in molecular size (kinetic diameter:
) And isobutylene (kinetic diameter:
) Will flow out from the bed layer; then, the pure component of the 1,3 butadiene can be obtained by elution in the bed layer through the next step of pressure swing regeneration desorption process; the regenerated biomass-based adsorption material is used for the next adsorption and separation process and is recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011377274.4A CN112499628A (en) | 2020-11-30 | 2020-11-30 | Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011377274.4A CN112499628A (en) | 2020-11-30 | 2020-11-30 | Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112499628A true CN112499628A (en) | 2021-03-16 |
Family
ID=74968147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011377274.4A Pending CN112499628A (en) | 2020-11-30 | 2020-11-30 | Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112499628A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113042025A (en) * | 2021-04-02 | 2021-06-29 | 福州大学 | Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436462A (en) * | 2019-07-29 | 2019-11-12 | 华南理工大学 | A kind of micro-pore carbon material and the preparation method and application thereof preparing highly selective separation propylene propane using starch |
-
2020
- 2020-11-30 CN CN202011377274.4A patent/CN112499628A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436462A (en) * | 2019-07-29 | 2019-11-12 | 华南理工大学 | A kind of micro-pore carbon material and the preparation method and application thereof preparing highly selective separation propylene propane using starch |
Non-Patent Citations (1)
| Title |
|---|
| 郝吉明等: "《大气污染控制工程》", 29 February 2004, 高等教育出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113042025A (en) * | 2021-04-02 | 2021-06-29 | 福州大学 | Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof |
| CN113042025B (en) * | 2021-04-02 | 2022-06-24 | 福州大学 | Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108751189B (en) | Preparation and application of aluminum-based MOF (metal organic framework) porous carbon material with high specific surface area | |
| CN100563829C (en) | Integral supported carbon molecular sieve catalyst and preparation method thereof is used | |
| WO1989004810A1 (en) | Activated carbon and process for its production | |
| CN110813365B (en) | Modification method of molecular sieve, modified molecular sieve and application | |
| CN109179369B (en) | Preparation method of carbon molecular sieve for adsorbing and separating methane and nitrogen by phenolic resin matrix | |
| JP5495208B2 (en) | High specific surface area activated carbon using lignin as raw material and adsorbent for lower alcohol containing the same | |
| CN113019318B (en) | Preparation method and application of carbon molecular sieve for separating olefin and alkane | |
| CN114272892B (en) | CO (carbon monoxide)2Trapping adsorbent and preparation method and application thereof | |
| CN112044401A (en) | Porous organic cage adsorbing material and preparation method thereof | |
| CN111530424B (en) | Copper-loaded modified carbon material adsorbent for efficiently removing gaseous benzene series and preparation method and application thereof | |
| CN113769715B (en) | Yttrium-based metal organic framework material and preparation method and application thereof | |
| CN110237823B (en) | Metal organic framework material with ethane preferential adsorption function and preparation method thereof | |
| CN112499628A (en) | Biomass-based porous carbon material, preparation method thereof and application of biomass-based porous carbon material in separation of 1, 3-butadiene from carbon tetraene mixture | |
| CN112940269B (en) | Copper-based metal organic framework material Cu-IPA for separating ethane and methane, and preparation method and application thereof | |
| CN110639474A (en) | Adsorbent for separating propylene and propane and preparation method thereof | |
| CN112023887B (en) | Preparation method of TNT @ Cu-BTC composite adsorbent and application of TNT @ Cu-BTC composite adsorbent in cyclohexane adsorption | |
| CN108311109A (en) | A kind of molasses adsorbing material and its preparation method and application | |
| CN110270231B (en) | MOF (Metal organic framework) derivative gas separation membrane as well as preparation method and application thereof | |
| CN113351163B (en) | Microporous carbon adsorbent for separating C6 alkane isomer and C8 xylene isomer, and preparation method and application thereof | |
| LU502475B1 (en) | Cu(I) LOADED MOLECULAR SIEVE ADSORBENT, PREPARATION METHOD THEREFOR, AND APPLICATIONS THEREOF | |
| AU2021102041A4 (en) | Nd-MOFs Gas adsorption material and its preparation method and application thereof | |
| CN115044050B (en) | Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof | |
| CN115888647B (en) | Nitrogen-doped particles with high acetylene adsorption selectivity and preparation method thereof | |
| CN114249628B (en) | CH3F and C3H8 separation method | |
| CN113583251B (en) | For NH 3 Copper-based MOF adsorbent for gas removal and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210316 |
|
| RJ01 | Rejection of invention patent application after publication |